2-iodo-N-trifluoromethylimidazole derivative and preparation method thereof

Abstract

The invention discloses a 2-iodo-N-trifluoromethylimidazole derivative and a preparation method thereof, and belongs to the technical field of compound synthesis. The preparation method of the 2-iodo-N-trifluoromethylimidazole derivative provided by the invention is simple, convenient and efficient, aryl isonitrile or alkyl isonitrile which is easy to obtain is used as a starting raw material, under the synergistic effect of silver fluoride (AgF) and N-iodo-succinimide (NIS), the reaction can be rapidly completed through a one-step method, and a target product is efficiently obtained. The prepared 2-iodo-N-trifluoromethylimidazole derivative has excellent structural stability, the 2-position iodine atom in the structure can be used as a high-activity leaving group or reaction site, and various compounds with important value in the field of medicine can be further derived conveniently and efficiently through subsequent conversion reaction.

Description

Technical Field

[0001] This invention belongs to the field of compound technology, and particularly relates to a 2-iodo-N-trifluoromethylimidazolium derivative and its preparation method. Background Technology

[0002] In medicinal chemistry, the introduction of trifluoromethyl groups is an effective strategy for enhancing the performance of active molecules. Specifically, compared to N-methyl analogs, N-trifluoromethyl imidazoles exhibit higher lipophilicity, metabolic stability, and Caco-2 permeability. Given the unique chemical structure and diverse biological activities of imidazole compounds, they are widely used in the development of various drugs, including antifungal, antiparasitic, anticancer, and antihypertensive drugs.

[0003] Currently, there are three main methods for synthesizing N-trifluoromethylbenzimidazole compounds: 1) In 2015, the Togni group activated imidazole nitrogen with a silicon group and then introduced a trifluoromethyl group using an electrophilic trifluoromethylating agent (Antonio Togni, Organometallics, 2015, 34, 7, 1384–1395); 2) In 2020, the Stefan group achieved the goal by gradually introducing fluorine-containing groups and performing halogen exchange. Benzimidazole was first nucleophilically substituted with difluorodibromomethane to introduce a bromodifluoromethyl group, followed by fluorine-halogen exchange (Stefan Schiesser, J. Med. Chem., 2020, 63, 21, 13076–13089); 3) In 2016, the Toste group successfully synthesized and applied a novel electrophilic trifluoromethylating agent of trifluoromethyl iodonium salt to achieve direct N-trifluoromethylation of benzimidazole under acid catalysis (F. Dean Toste, ACS). Cent. Sci., 2016, 2, 5, 341–350).

[0004] However, the existing methods for synthesizing N-trifluoromethylimidazolium compounds have the following drawbacks: Method 1) requires pre-activation of the nitrogen atom of benzimidazole via silanization; Method 2) uses difluorodibromomethane (CF2Br2), a halomethane, which is toxic and causes environmental pollution; Method 3) requires the synthesis of ammonium iodide salts as a phase transfer catalyst. All three methods are cumbersome and time-consuming, increasing the overall complexity and reaction time, resulting in generally low overall yields and low efficiency of the final products. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a 2-iodo-N-trifluoromethylimidazolium derivative and its preparation method.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing a 2-iodo-N-trifluoromethylimidazolium derivative, comprising the following steps: dissolving aryl isonitriles or alkyl isonitriles, silver fluoride and N-iodosuccinimide (NIS) in an organic solvent to carry out a one-step reaction to obtain the 2-iodo-N-trifluoromethylimidazolium derivative.

[0008] Furthermore, the molar ratio of the aryl isonitrile or alkyl isonitrile, silver fluoride and N-iodosuccinimide is 1:7:2.

[0009] Furthermore, the temperature of the one-step reaction is room temperature, and the reaction time is 10 minutes.

[0010] Further, the aryl isonitrile is selected from 1,2-diisocyanobenzene, 1,2-diisocyano-4,5-dimethylbenzene, 2,3-diisocyanonaphthalene, 2',3'-diisocyano-1,1':4',1''-terphenyl, 2',3'-diisocyano-4,4''-bis(trifluoromethyl)-1,1':4',1''-terphenyl, 2',3'-diisocyano-4,4''-dimethyl-1,1':4',1''-terphenyl, 2',3'-diisocyano-3,3''-dimethyl-1,1' :4',1''-terphenyl, 2,2'-(2,3-diisocyano-1,4-phenylene)dithiophene, 4',5'-diisocyano-1,1':2',1''-terphenyl, 4',5'-diisocyano-3,3''-dimethyl-1,1':2',1''-terphenyl, 4',5'-diisocyano-4,4''-dimethyl-1,1':2',1''-terphenyl or 4',5'-diisocyano-[1,1':2',1''-terphenyl]-4,4''-dicyano;

[0011] The alkyl isonitrile is selected from 1,2-diisocyano-1,2-diphenylethane.

[0012] This invention also provides a 2-iodo-N-trifluoromethylimidazole derivative prepared according to the preparation method described above, wherein the structural formula of the 2-iodo-N-trifluoromethylimidazole derivative is: Wherein, R is aryl, fused-ring aryl, or alkyl.

[0013] Furthermore, the aryl group is selected from polysubstituted phenyl groups.

[0014] Furthermore, the fused-ring aryl group is selected from naphthalene rings.

[0015] Furthermore, the alkyl group is selected from methyl.

[0016] Furthermore, the structural formula of the 2-iodo-N-trifluoromethylimidazolium derivative is as follows: , , , , , , , , , , , or .

[0017] Compared with the prior art, the present invention has the following advantages and technical effects:

[0018] The preparation method of 2-iodo-N-trifluoromethylimidazolium derivative provided by this invention is simple and efficient. It uses readily available aryl isonitriles or alkyl isonitriles as starting materials. With the synergistic effect of silver fluoride (AgF) and N-iodosuccinimide (NIS), the reaction can be completed rapidly in one step, and the target product can be obtained with high efficiency.

[0019] The 2-iodo-N-trifluoromethylimidazolium derivative prepared by this invention has excellent structural stability, and the iodine atom at the 2-position in the structure can serve as a highly active leaving group or reaction site. Through subsequent transformation reactions, it can be conveniently and efficiently derived into various compounds of important value in the pharmaceutical field. Attached Figure Description

[0020] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0021] Figure 1 The reaction route diagrams are shown for the synthesis of three existing N-trifluoromethylbenzimidazole compounds.

[0022] Figure 2 This is a reaction mechanism diagram for the preparation of compound 2a in Example 1 of the present invention;

[0023] Figure 3 This is an X-ray diffraction pattern of compound 2a prepared in Example 1 of the present invention. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0026] In this embodiment of the invention, room temperature refers to "25±2℃".

[0027] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased through commercial channels.

[0028] Example 1

[0029] The preparation process of compound 2a is as follows:

[0030] 1,2-diisocyanobenzene (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. After stirring at room temperature for 10 min, the resulting reaction solution was filtered through diatomaceous earth, and then the diatomaceous earth was washed with 10 mL of ethyl acetate. The resulting wash and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 30:1), yielding a pale yellow solid compound 2a in 63% yield.

[0031] The structural formula of compound 2a is: .

[0032] The NMR and high-resolution characterization of compound 2a yielded the following results: 1 H NMR (400 MHz, Chloroform-d) δ 7.80 – 7.70 (m, 1H), 7.63 – 7.54 (m, 1H), 7.41 – 7.30 (m, 2H). 19 F NMR (376 MHz, Chloroform-d) δ -51.85 (d, J = 2.0 Hz). 13 C NMR (126MHz, Chloroform-d) δ 145.18, 134.00, 125.60, 124.70, 120.11, 119.03 (q, J =266.40 Hz) 111.90 (q, J = 4.7 Hz), 92.05. HRMS (ESI): calc. for [M+H;C8H5F3IN2 + ]: 312.9444; found: 312.9420.

[0033] The reaction mechanism for the preparation of compound 2a in Example 1 is as follows: Figure 2 As shown, the specific reaction mechanism is as follows: NIS oxidizes isonitrile to α-iodoimine ions. One of the imine ions undergoes a displacement reaction with silver fluoride in the system to generate the intermediate difluoroimine. The difluoro portion is further attacked by another fluoride ion to generate trifluoromethylamine or its anion. Subsequently, it rapidly undergoes intramolecular cyclization to obtain compound 2a.

[0034] The X-ray diffraction pattern of compound 2a prepared in Example 1 is shown in Figure 1. Figure 3 .from Figure 3 As can be seen, compound 2a was successfully synthesized in Example 1.

[0035] Example 2

[0036] The preparation process of compound 2b is as follows:

[0037] 1,2-diisocyano-4,5-dimethylbenzene (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1), yielding a pale yellow solid compound 2b in 65% yield.

[0038] The structural formula of compound 2b is: .

[0039] The NMR and high-resolution characterization of compound 2b yielded the following results: 1 H NMR (400 MHz, Chloroform-d) δ 7.48 (s, 1H), 7.35 (s, 1H), 2.38 (s, 3H), 2.35 (s, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -51.90 (d, J = 2.0 Hz). 13C NMR (101 MHz, Chloroform-d) δ 143.78, 135.03, 133.74, 132.47, 119.95, 119.04 (, J = 265.7Hz), 112.07 (q, J = 4.5 Hz), 90.38, 20.71, 20.20. HRMS (ESI): calc. for [M+H;C 10 H9F3IN2 + ]: 340.9757; found: 340.9794.

[0040] Example 3

[0041] The preparation process of compound 2c is as follows:

[0042] 2,3-diisocyanonaphthalene (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. After stirring at room temperature for 10 min, the resulting reaction solution was filtered through diatomaceous earth, and then the diatomaceous earth was washed with 10 mL of ethyl acetate. The resulting wash and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 30:1), yielding a white solid compound 2c in 54% yield.

[0043] The structural formula of compound 2c is: .

[0044] The NMR and high-resolution characterization of compound 2c yielded the following results: 1 H NMR (500 MHz, Chloroform-d) δ 8.20 (s, 1H), 8.01 – 7.98 (m, 2H), 7.94 (dd, J = 7.7, 1.9 Hz, 1H), 7.56 – 7.46 (m, 2H). 19 F NMR (376 MHz, Chloroform-d) δ -51.73 (d, J = 1.9Hz). 13C NMR (126 MHz, Chloroform-d) δ 144.26, 132.93, 131.39, 130.83, 128.69,128.11, 126.37, 125.54, 119.26 (q, J = 265.8 Hz), 117.51, 108.71 (q, J = 4.8Hz), 96.61.HRMS (ESI): calc. for [M+H; C 12 H8F3IN2 + ]: 362.9601; found: 362.9579.

[0045] Example 4

[0046] The preparation process of compound 2d is as follows:

[0047] 2',3'-diisocyano-1,1':4',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 50:1), yielding a white solid compound 2d in 65% yield.

[0048] The structural formula of compound 2d is: .

[0049] The compound 2d was characterized by NMR and high-resolution imaging, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.90 (dd, J = 7.0, 1.6 Hz, 1H), 7.54 - 7.50 (m, 3H), 7.45 -7.40 (m, 6H), 7.28 (dd, J = 7.9, 1.3 Hz, 1H). 19 F NMR (376 MHz, Chloroform-d)δ -47.00. 13C NMR (101 MHz, Chloroform-d) δ 143.84, 139.77 (q, J = 2.3 Hz), 137.03, 132.90, 132.06, 129.64, 128.92, 128.71, 128.54 (q, J = 1.8 Hz),128.42, 128.14, 127.83, 127.33, 124.36, 118.16 (, J = 268.3 Hz), 93.38. HRMS(ESI): calc. for [M+H; C 20 H 13 F3IN2 + ]: 465.0070; found: 465.0041.

[0050] Example 5

[0051] The preparation process of compound 2e is as follows:

[0052] 2',3'-diisocyano-4,4''-bis(trifluoromethyl)-1,1':4',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 50:1), yielding a white solid compound 2e in 60% yield.

[0053] The structural formula of compound 2e is: .

[0054] The NMR and high-resolution characterization of compound 2e yielded the following results: 1 H NMR (400 MHz, Chloroform-d) δ 8.01 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 8.2 Hz, 2H), 7.73 (d,J = 8.0 Hz, 2H), 7.54 (dd, J = 8.0, 1.8 Hz, 3H), 7.28 (d, J = 7.9 Hz, 1H).19 FNMR (376 MHz, Chloroform-d) δ -47.09, -62.51, -62.57. 13 C NMR (126 MHz, Chloroform-d) δ 144.00, 143.10, 140.28 (q, J = 1.4 Hz), 132.66, 131.23, 130.31 (q, J = 32.5 Hz), 130.22 (q, J = 32.3 Hz), 129.93, 128.95 (q, J = 2.1Hz), 128.80, 126.56, 125.70 (q, J = 3.8 Hz), 125.53 (q, J = 3.7 Hz), 124.51,124.37 (q, J = 272.1 Hz), 124.22 (q, J = 272.1 Hz), 118.06 (q, J = 268.3 Hz),94.02. HRMS (ESI): calc. for [M+H; C 22 H 11 F9IN2 + ]: 600.9818; found: 600.9778.

[0055] Example 6

[0056] The preparation process of compound 2f is as follows:

[0057] 2',3'-diisocyano-4,4''-dimethyl-1,1':4',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 20:1), yielding a colorless liquid compound 2f in 92% yield.

[0058] The structural formula of compound 2f is: .

[0059] The compound 2f was characterized by NMR and high-resolution imaging, and the results are as follows:1 H NMR (500 MHz, Chloroform-d) δ 7.69 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 7.9 Hz, 1H), 7.22 (d,J = 7.9 Hz, 2H), 7.19 (d, J = 7.8 Hz, 2H), 7.15 (d, J = 5.1 Hz, 2H), 7.13 (d,J = 4.6 Hz, 1H), 2.33 (s, 6H). 19 F NMR (376 MHz, Chloroform-d) δ -46.81. 13 CNMR (126 MHz, Chloroform-d) δ 143.83, 137.93, 137.50, 136.94 (q, J = 2.2 Hz), 134.17, 132.99, 131.86, 129.47, 129.42, 129.08, 128.95, 128.37 (q, J = 1.9Hz), 127.10, 124.09, 118.20 (q, J = 267.9 Hz), 93.17, 21.41. HRMS (ESI):calc. for [M+H; C 22 H 17 F3IN2 + ]: 493.0383; found: 493.0363.

[0060] Example 7

[0061] The preparation process of compound 2g is as follows:

[0062] 2',3'-diisocyano-3,3''-dimethyl-1,1':4',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The washing solution and filtrate were combined and purified by vacuum distillation under reduced pressure and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 50:1). 2 g of a white solid compound was obtained, with a yield of 82%.

[0063] The structural formula of compound 2g is: .

[0064] The compound 2g was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.64 – 7.54 (m, 2H), 7.39 (dd, J = 7.8, 3.1 Hz, 1H), 7.32(td, J = 7.6, 3.0 Hz, 1H), 7.25 (td, J = 7.5, 3.0 Hz, 1H), 7.18 (dd, J = 7.8, 3.0 Hz, 1H), 7.14 (dd, J = 9.5, 5.8 Hz, 4H), 2.37 (s, 3H), 2.33 (s, 3H). 19 FNMR (376 MHz, Chloroform-d) δ -46.91. 13 C NMR (126 MHz, Chloroform-d) δ143.83, 139.72, 138.20, 138.05, 137.02, 132.91, 132.14, 130.24, 129.23,128.91, 128.76, 128.59, 128.48, 128.33, 127.40, 126.85, 125.53, 124.42,118.20 (q, J = 268.3 Hz), 93.38, 21.78, 21.52. HRMS (ESI): calc. for [M+H;C 22 H 18 F3IN2 + ]: 493.0383; found: 493.0351.

[0065] Example 8

[0066] The preparation process of compound 2h is as follows:

[0067] 2,2'-(2,3-diisocyano-1,4-phenylene)dithiophene (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. After stirring at room temperature for 10 min, the resulting reaction solution was filtered through diatomaceous earth, and then the diatomaceous earth was washed with 10 mL of ethyl acetate. The resulting wash and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1). A pale yellow solid compound was obtained after 2 h, with a yield of 65%.

[0068] The structural formula of compound 2h is: .

[0069] The compound 2h was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.05 (dd, J = 3.7, 1.2 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.43 (dd, J = 5.1, 1.1 Hz, 1H), 7.39 (dd, J = 4.9, 1.5 Hz, 1H), 7.32 (d, J =7.9 Hz, 1H), 7.19 (dd, J = 5.1, 3.7 Hz, 1H), 7.12 – 7.04 (m, 2H). 19 F NMR (376MHz, Chloroform-d) δ -47.60. 13 C NMR (126 MHz, Chloroform-d) δ 142.63, 139.70(q, J = 2.6 Hz), 138.68, 137.69, 133.70, 130.10, 128.07, 127.85, 127.24 (q, J= 2.4 Hz), 127.06, 126.90, 125.96, 122.06, 119.09, 118.11 (q, J = 268.5 Hz),93.13. HRMS (ESI): calc. for [M+H; C 16 H9F3IN2S2 + ]:476.9199; found: 476.9173.

[0070] Example 9

[0071] The preparation process of compound 2i is as follows:

[0072] 1,2-Diisocyano-1,2-diphenylethane ((1S,2S)-1,2-diisocyano-1,2-diphenylethane, 0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. After stirring at room temperature for 10 min, the resulting reaction solution was filtered through diatomaceous earth, and then the diatomaceous earth was washed with 10 mL of ethyl acetate. The resulting wash solution and filtrate were combined and purified by vacuum distillation under reduced pressure and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1), yielding a yellow solid compound 2i in 48% yield.

[0073] The structural formula of compound 2i is: .

[0074] The compound 2i was characterized by NMR and high-resolution imaging, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.43 – 7.32 (m, 6H), 7.28 – 7.23 (m, 2H), 7.19 – 7.13 (m,2H), 5.00 (d, J = 7.3 Hz, 1H), 4.78 (dq, J = 7.4, 1.4 Hz, 1H). 19 F NMR (376MHz, Chloroform-d) δ -52.59 (d, J = 1.9 Hz). 13 C NMR (101 MHz, Chloroform-d) δ140.18, 140.16, 129.29, 129.12, 128.73, 128.45, 126.57, 126.19, 120.31 (q, J= 263.2 Hz), 105.51, 82.12, 71.34. HRMS (ESI): calc. for [M+H; C 16 H 13 F3IN2 + ]:417.0070; found: 417.0045.

[0075] Example 10

[0076] The preparation process of compound 2j is as follows:

[0077] 4',5'-diisocyano-1,1':2',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1), yielding a white solid compound 2j with a yield of 57%.

[0078] The structural formula of compound 2j is: .

[0079] The compound 2j was characterized by NMR and high-resolution imaging, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.80 (s, 1H), 7.63 (s, 1H), 7.25 – 7.20 (m, 6H), 7.16 – 7.13 (m, 4H). 19 F NMR (376 MHz, Chloroform-d) δ -51.76 (d, J = 1.9 Hz). 13 C NMR(126 MHz, Chloroform-d) δ 144.61, 141.11, 140.85, 139.09, 138.29, 133.40,130.21, 128.12 (d, J = 2.7 Hz), 127.04, 126.88, 121.34, 119.03 (q, J = 266.5Hz), 113.48 (q, J = 4.6 Hz), 92.52. HRMS (ESI): calc. for [M+H; C 20 H 13 F3IN2 + ]:465.0070; found: 465.0046.

[0080] Example 11

[0081] The preparation process of compound 2k is as follows:

[0082] 4',5'-diisocyano-3,3''-dimethyl-1,1':2',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane were added to a Schlenk tube. The mixture was stirred at room temperature for 10 min. The resulting reaction solution was filtered through diatomaceous earth, and the diatomaceous earth was washed with 10 mL of ethyl acetate. The wash solution and filtrate were combined and purified by vacuum distillation and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1), yielding a white solid compound 2k in 87% yield.

[0083] The structural formula of compound 2k is: .

[0084] The compound 2k was characterized by NMR and high-resolution imaging, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.78 (s, 1H), 7.62 (q, J = 1.9 Hz, 1H), 7.09 (td, J = 7.5,2.4 Hz, 2H), 7.02 (dd, J = 16.1, 5.3 Hz, 4H)., 6.89 (dd, J = 7.5, 1.7 Hz,2H), 2.28 (s, 3H), 2.27 (s, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -51.74. 13 CNMR (101 MHz, Chloroform-d) δ 144.51, 141.08, 140.80, 139.23, 138.40, 137.69,137.62, 133.30, 130.88, 130.80, 127.85, 127.83, 127.69, 127.53, 127.38,127.36, 121.19, 119.04 (q, J = 266.2 Hz), 113.33 (q, J = 4.6 Hz), 92.35,21.50. HRMS (ESI): calc. for [M+H; C 22 H 17 F3IN2 +]:493.0383; found: 493.0353.

[0085] Example 12

[0086] The preparation process of compound 2l is as follows:

[0087] Add 4',5'-diisocyano-4,4''-dimethyl-1,1':2',1''-terphenyl (0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane to a Schlenk tube. Stir at room temperature for 10 min. Filter the resulting reaction solution with diatomaceous earth, then wash the diatomaceous earth with 10 mL of ethyl acetate. Combine the wash and filtrate, and purify by vacuum drying under reduced pressure and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 10:1), yielding 2 μL of a white solid compound in 68% yield.

[0088] The structural formula of the compound is: .

[0089] The compound 2l was characterized by nuclear magnetic resonance and high-resolution characterization, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.77 (s, 1H), 7.60 (q, J = 1.8 Hz, 1H), 7.05 (s, 4H), 7.05(s, 4H), 2.33 (s, 3H), 2.33 (s, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -51.79. 13 C NMR (101 MHz, Chloroform-d) δ144.51, 139.04, 138.33, 138.21, 138.06,136.67, 136.46, 133.29, 130.02, 128.88, 128.87, 121.31, 119.05 (q, J = 266.3Hz), 113.44 (q, J = 4.6 Hz), 92.24, 21.25. HRMS (ESI): calc. for [M+H;C 22 H 18 F3IN2 +]:493.0383; found: 493.0361.

[0090] Example 13

[0091] The preparation process of compound 2m is as follows:

[0092] Add 4',5'-diisocyano-[1,1':2',1''-terphenyl]-4,4''-dicyano(4',5'-diisocyano-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile, 0.1 mmol, 1.0 equiv), silver fluoride (0.7 mmol, 7.0 equiv), NIS (0.2 mmol, 2.0 equiv), and 2 mL of 1,2-dichloroethane to a Schlenk tube. Stir at room temperature for 10 min. Filter the resulting reaction solution with diatomaceous earth, then wash the diatomaceous earth with 10 mL of ethyl acetate. Combine the wash and filtrate, and purify by vacuum drying under reduced pressure and silica gel column chromatography. The eluent for purification was a mixture of petroleum ether and ethyl acetate (volume ratio 5:1), yielding a pale yellow solid compound 2 M, with a yield of 42%.

[0093] The structural formula of compound 2m is: .

[0094] The compound 2m was characterized by NMR and high-resolution imaging, and the results are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.79 (s, 1H), 7.62 (q, J = 1.6 Hz, 1H), 7.56 (d, J = 8.3 Hz, 2H), 7.55 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 7.8 Hz, 2H), δ 7.21 (d, J = 7.9Hz, 2H). 19 F NMR (376 MHz, Chloroform-d) δ -51.77. 13 C NMR (101 MHz, Chloroform-d) δ 145.25, 145.06, 144.85, 136.74, 133.99, 132.27, 130.86,130.82, 121.73, 118.90 (q, J = 266.9 Hz), 118.53, 118.48, 113.76 (q, J = 4.7Hz), 94.24. HRMS (ESI): calc. for [M+H; C 22H 11 F3IN4 + ]:514.9975; found:514.9949.

[0095] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a 2-iodo-N-trifluoromethylimidazolium derivative, characterized in that, Includes the following steps: The 2-iodo-N-trifluoromethylimidazolium derivative is obtained by dissolving aryl isonitriles or alkyl isonitriles, silver fluoride and N-iodosuccinimide in an organic solvent in a one-step reaction.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the aryl isonitrile or alkyl isonitrile, silver fluoride and N-iodosuccinimide is 1:7:

2.

3. The preparation method according to claim 1, characterized in that, The reaction in the first step was carried out at room temperature for 10 minutes.

4. The preparation method according to claim 1, characterized in that, The aryl isonitrile is selected from 1,2-diisocyanobenzene, 1,2-diisocyano-4,5-dimethylbenzene, 2,3-diisocyanonaphthalene, 2',3'-diisocyano-1,1':4',1''-terphenyl, 2',3'-diisocyano-4,4''-bis(trifluoromethyl)-1,1':4',1''-terphenyl, 2',3'-diisocyano-4,4''-dimethyl-1,1':4',1''-terphenyl, 2',3'-diisocyano-3,3''-dimethyl-1,1': 4',1''-terphenyl, 2,2'-(2,3-diisocyano-1,4-phenylene)dithiophene, 4',5'-diisocyano-1,1':2',1''-terphenyl, 4',5'-diisocyano-3,3''-dimethyl-1,1':2',1''-terphenyl, 4',5'-diisocyano-4,4''-dimethyl-1,1':2',1''-terphenyl or 4',5'-diisocyano-[1,1':2',1''-terphenyl]-4,4''-dicyano; The alkyl isonitrile is selected from 1,2-diisocyano-1,2-diphenylethane.

5. A 2-iodo-N-trifluoromethylimidazolium derivative prepared by the method according to any one of claims 1 to 4, characterized in that, The structural formula of the 2-iodo-N-trifluoromethylimidazol derivative is: Wherein, R is aryl, fused-ring aryl, or alkyl.

6. The 2-iodo-N-trifluoromethylimidazolium derivative according to claim 5, characterized in that, The aryl group is selected from polysubstituted phenyl groups.

7. The 2-iodo-N-trifluoromethylimidazolium derivative according to claim 5, characterized in that, The fused-ring aryl group is selected from naphthalene rings.

8. The 2-iodo-N-trifluoromethylimidazolium derivative according to claim 5, characterized in that, The alkyl group is selected from methyl.

9. The 2-iodo-N-trifluoromethylimidazolium derivative according to claim 5, characterized in that, The structural formula is: , , , , , , , , , , , or .

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